Octylphenols and ethers thereof



Patented Jan. 8, 1935 UNITED STATES 1,987,228 p oomrnsuops AND s'rnnas THEREOF,

'Herman A. Bruson,

Philadelphia, Pa., assignor to The Rcsinous Products & Chemical Company,

Inc., Philadelphia, Pa.

No Drawing. Application November 14, 1933,

Serial No. 697,928

This invention relates to condensation products of phenols or phenyl ethers with mixed dipolymersof the three isomeric butylenes, boiling within a range of 106-123 C. at 760 m m.

In the vapor phase cracking of petroleum to form gasoline, considerable quantities of the three isomeric butylenes mixed with butane are obtained. This gaseous mixture has very little commercial value at the present time except as a substitute for illuminating gas. It contains about 45% by'weight or butenes and 55% of butane. Approximately 15% is isobutylene and 30% is a mixture of butene-l and butane-2. Upon treatment with concentrated sulfuric acid, the three isomericbutylenes polymerize and condense with each other to form a complex mixture of higher molecular olefines boiling from about C. to 200 C. at 760 m. m.

Upon carefully fractionating such a mixture of polymers and condensation products of the three isomeric butylenes, an olefine (octene) fraction is obtained which boils at 106-123 C. (760 m. m.) This fraction is substantially free from. diisobutylene and tri-isobutylene. Most of it boils at 106-116 C. (.760 m. m.) It is also free from straight-chained oleflnes.

The above octene fraction of boiling range 106-123 C. 'or 106-116 C. is very reactive and according to the present invention combines readily with phenols having free ortho or para positions to the hydroxyl group, in the presence of a small quantity of concentrated sulfuric acid as a catalyst, so as to alkylate such free nuclear positions. The products form a mixture the individual components of which possess the general formula CsHi7R--OH where CsHrt represents a branched-chain octyl group other than the alpha, alpha, gamma, gamma-tetramethyl-butyl group, and R represents an aromatic hydrocarbon ring which can be either monocyclic or polycyclic, and which can contain nuclear halogen, hydroxyl, alkoxy-, alkyl-, aryl-, aryloxy-, carboxyl, or nitro groups. By condensing phenyl ethers such as anisol, phenetol, diphenyloxide, or guaicol witli' the dibutene'fraction of boiling range 106-116 C.

or 106-123" C., the nuclear 'octyl substituted ethers can be obtained of the formula CsHrz-R0-X where X is a hydrocarbon radical of the original ether.

It is already known in the prior art that olefines will condense with phenols to form nuclear alkylated phenols. Propylene, butylenes, amylene cyclohexene, diamylene, diisobutylene, styrene, and indene have thus been condensed with phenols to form nuclear substituted phenols. In

20-35% of the total polymeric mixture.

to prevent resinification most of these cases undesirable ethers are formed which must be separated from the phenols. If octene-l or octene-2 (or a mixture of the two) is used in place of the oleflnes heretofore employed in condensations with phenol, only traces of octylphenol are obtained regardless of the methods used. The only octylphenol which it has heretofore been possible to prepare in good yield by direct condensation of an olefine with phenol is the alpha, alpha, gamma, gamma-'tetramethylbutyl-phenol from diisobutylene and phenol. (Niederl, J. Am. Chem. Soc. 55, 2571 (1933)).

One of the objects of the present invention is to prepare an isomeric mixture of new octylphenols and ethers of octylphenols by polymerizing the mixture of the three butylene isomers from petroleum cracking operations, by means of sulfuric acid, fractionating therefrom a specific dibutene mixture boiling within the range of 106- 123 C. which is substantially free from the wellknown diisobutylene, and condensing said dibutene of boiling range IDS-123 C. or 106-116 'C. with phenols or phenol ethers through the agency of a small quantity of concentrated sulfuric acid as a catalyst. By this method new octylphenolscan be prepared in high yield and purity at a veryv low cost. Such new octylphenols can'be used as germicide's and antiseptics in soaps and in oils; as antioxidants in rubbengasoline, soaps and vegetable oils; as raw materials for making resins by condensation with formaldehyde, furfural, and other aldehydes, and as plasticizers for resinous compositions. They have the advantage over the octylphenols made from diisobutylene of a lower cost of production,,because of the greater availability of the olefine, since the quantity of diisobutylene obtained by co-polymerizing a mixture of the three isomeric butylenes as they occur in the cracked distillate is only about 1 of the total butylene polymers whereas the quantity of the dibutene fraction of boiling range 106-123 C. is These new octylphenols are isomeric, but not identical with the knownoc ylphenols prepared from diisobutylene.

The condensation between phenols and the dibutenes of boiling range 106-423 C. or 106-116 C. is preferably carried out by adding concentrated sulfuric acid slowly, and with stirring, to the mixture at a temperature below 50 (3.; advantageously at 28-35 C. Alternatively the suli'uric acid can be mixed with the olefine, and the phenol added thereto, or vice versa, but this procedure requires a very much lower temperature and leads to considerable best results should be 93-96% H2804. A very important factor is the quantity of 96% 111804 used. This should be preferably. though not necessarily, an amount corresponding to 0.13-0.30

mol H2804 per mol of dibutene, and is most advantageously 0.18 mol H2804 per mol of dibutene. Suitable phenols for the herein described condensation with dibutenes are phenol itself, betanaphthol, resorcinol, pyrocatechol, hydroquinone,

- alkylated phenols, such as o-, m-, or p-cresol, xylenols, isopropylphenols, halogenated phenols such as m-chlorphenol, nitrophenols, salicylic acid, p-hydroxybenzoic acid; also phenol ethers such as anisole, phenetol, guaicol, diphenyl ether and their obvious equivalents.

The products obtained by condensing any of the above phenols or phenyl ethers with dibutene as herein specified are probably mixtures of several isomeric nuclear octyl derivatives of the phenols or phenyl ethers employed since the dibutenes used are a mixture of several branched chain octenes. The products, however, boil within a very narrow range.

The following examples are given by way of illustration and not limitation.

, Example 1 (a) 94 grams of phenol are mixed with 112 grams of a dibutene fraction 3. P. 100-110 C. (160 m. m.) prepared as described above. The

is cooled to C. and with rapid stirring a few drops of 98% sulfuric acid are added. The tem- 40 perature tends to rise but is controlled by surrounding the vessel with cold water, so that the temperature during the addition of the sulfuric acid remains at about 28-32 C. A total of 18 grams of 96%-HzSOiis runin during thecourse as of 1 hour. The mixture is then allowed to stand at ordinary room temperature (25C.) for 0-24 hours to complete the reaction. The brown 011 obtained is mixed with 3 liters of water containing slightly more than the theoretical quantity so of sodium hydroxide required to neutralize the acid and the mixture'heated to 90 C. with stirring for a short time so as to completely neutralize all of the free acidity. The oil layer is separated, washed with water, and .distilled under as reduced pressure. The octylphenol came over as a colorless oil at 137-142 C. under 2 m. m. pressure of mercury. Upon cooling it solidified to a waxy crystalline mass. The yield was about 05% of theory.

(b) Similarly 94 grams of phenol were condensed with 112 grams of a dibutene fraction of boiling range 116123 C. as prepared by polymerizing a mixture of the three isomeric butylenes and fractionating out any diisobutylene. Upon working 05 up the condensate as in (a) 122 grams of colorless crystalline product boiling I at 189-143 C. under 3'm.'m.

Example 2 mamas there was obtainedby polymerization of the bonate solution suflcient to neutralize any free acidity. The washed, neutral oil was then purifled by distillation in vacuo. It formed a oolorless somewhat viscous oil which upon redistillation boiled at 127-131 C. under 2 m. m. pressure. 5

Inasimilarmannerm-orp-cresolcanbecon densed with dibutene. (b) The condensation product of resorcinol and the dibutene formed a'viscous yellow oil boiling at 156-175 C. under 3 m.m.

Imple 3 108 grams anisoi' (methylphenyl ether) was mixed with 112 grams of dibutene of boiling range 106-116 C. and 18 grams of 90% H1804 added dropwise during 1 hour with constant stirring. The temperature was kept at 28-32 C. duringtheadditionoftheacid. Themixturewas then allowed to stand 24hoursat room temperature and worked up by washing and distillation in vacuo as describedin Example 1. Octylanisol came over as a thin oil boiling at 115-420 C. under 2 m. m. mercury'pressure.

The above examples are typical of the method for preparing octylphenols and octyiaryi ethers by condensing, respectively, a member of group consisting of phenols and aryl others with dipoiymers of the mixed butylenes other than diisobutylene in the presence of concentrated sulfuric acid as a catalyst.

Any of the other phenols enumerated herein can be used molefor mole in place of-those speciiied in the examples.

Although in the above examples it is preferable to employ sulfuric acid in amounts subas stantiaily less than a molecular equivalent mixture amount, greateramountacanbeusedifdesired.v

Likewisethe otheringredientscanbevarledas well as the condition of operation, temperamres, etc.,' all within the spirit of the invention the scope of which islimited onlyby claims, it being understood that no modification of'the invention isclaimedtotheexclusionofanyothermodiiication. a

What I claim is:

Llntheprocessformakingmixedisome'ric octylphenols and ethers thereof. the step which consists inreactingrespectively amemberoithe group consisting of phenols having a tree ortho or para position to the hydroxyl group and ethers thereof, in the presence of concentrated sulfuric acid as a catalyst, with mixed octenes boiling within the range of 100-123 C.. said octenes being derived by polymerization of a mixture of the threeisomeric butenes irom cracked petroleum distillates.

2. A condensation product of a phenol and. mixed octenes which boil-within the range of 100-122 C. and which are derived by polymerization of the mixed butenes from'cracked distillates, said condensation, product being a mixture of isomeric octylphenols.

3. A condensation product of phenol and mixed octenes boiling at 100-116" C. which are derived by polymerization of the mixed butenes from cracked petroleum distillates, said condensation product being a colorless, crystalline mass boiling at 187-442 C. at 2 m. m. v

4. A condensation product of phenol and mixed octenes boiling at 116-123 c. which are derived mixed butenes from cracked petroleum distillates. said condensation product being a colorless, crystalline mass boiling at 139-143 C. at 3 m. m.

mixed octenes boiIing at 106-116 C. which are derived by polymerization of the mixed butenes from cracked petroleum distillates, said condensation product being a colorless oil boiling at 127-131" C. at 1 to 2 m. m.

6. In the process for making mixed isomeric octylphenols, the step which consists in reacting 1 mol. equivalent of a phenol having a free ortho or para position to the hydroxyl group with at least 1 mol. equivalent of mixed octenes boiling within the range of 106-123 C. which are derived by polymerization of the mixed butenes from cracked petroleum distillates, in the presence 01' concentrated sulfuric acid a catalyst at a temperature below 50 C.

'1. A process as set forth in claim 6, in which the sulfuric acid used is of 93-96% H2804 content,

in an amount equal to about 0.13-0.30 mol. H2804 per mol. of the octenes employed.

8. The process which consists in reacting 1 mol. equivalent of phenol with 1 mol. equivalent of mixed octenes boiling at 106-1l6 C. which are derived by polymerization of the mixed butenes from cracked petroleum distillates, in the presence of about 0.18 mol. 95-96% sulfuric acid at a temperature of 28-32 C.

HERMAN A. BRUSON. 

